N-(3-trifluoromethyl-4-chlorophenyl)-carbamates

ABSTRACT

THE INVENTION RELATES TO COMPOUNDS OF THE GENERAL FORMULA   (3-CF3,4-CL-PHENYL)-NH-COO-R1   WHEREIN R1 REPRESENTS AN ARALKYL OR ARALKENYL RESIDUE OR A PHENYL RADICAL HAVING 4 OR 5 SUBSTITUENTS OR A 5- TO 6MEMBERED HETEROCYCLE WHICH MAY BE BOUND OVER AN ALKYL RESIDUE. THE COMPOUNDS ARE USED FOR COMBATING VARIOUS TYPES OF PESTS, PREFERABLY BACTERIA AND FUNGI.

United States Patent 3,772,386 N-[3-TRIFLUOROMETHYL-4-CHLOROPHENYL1-CARBAMATES Adolf Hubele, Riehen, and Otto Rohr, Therwil, Switzerland,assignors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Originalapplication Feb. 4, 1969, Ser. No.

796,571, now Patent No. 3,676,457. Divided and this application May 30,1972, Ser. No. 258,119 Claims priority, application Switzerland, Feb. 6,'1968, 1,765/68 Int. Cl. C07c 125/06 US. Cl. 260-471 C 3 Claims ABSTRACTOF THE DISCLOSURE The invention relates to compounds of the generalformula ClQ-NE-C 0-0-Ri wherein R represents an aralkyl or aralkenylresidue or a phenyl radical having 4 or 5 substituents or a 5- to 6-membered heterocycle which may be bound over an alkyl residue. Thecompounds are used for combating various types of pests, preferablybacteria and fungi.

This is a division of application Ser. No. 796,571 filed on Feb. 4, 1969now Pat. No. 3,676,457.

The present invention provides pesticidal preparations, especiallypreparations of combating bacteria and fungi, which comprise, as activecomponent, a compound of the formula orQ-un-a 0-0-R1 in which Rrepresents an aralkyl or aralkenyl radical or a phenyl radical havingfour or five substituents selected from halogen, an alkyl, alkoxy and/ornitro group, or a 5- to o-membered heterocyclic radical that may beoptionally bound over an alkyl radical. The preparation may contain oneor more of the following additives: a solvent, a diluent, a dispersant,a weting agent, an adhesive as well as other known pesticides,

In a narrower sense, compounds of Formula I are used as activesubstances in which R represents a benzyl radical optionally substitutedby halogen and/or -NO or a phenyl radical having 4 to 5 substituentsselected from halogen, an alkyl, alkoxy and/or nitro group or a 5- to6-membered heterocyclic radical that is bound over an alkyl radical.

As examples of especially active groups for combating bacteria and fungithose of Compound II may be mentioned:

in which n=4 or 5 and Z represents the substituents CH --OCH -Cl, Br, NOwhich may be the same or ditferent from one another.

Among these, th ecompounds of the formulae 31,772,386 Patented Nov. 13,1973 0 F3 mQ-mrw 0-0 l or in which n=0 or 1 and R represents an aromaticradical.

The active substances of Formula I have an outstanding effectivenessagainst plant-pathogenic bacteria and fungi, e.g. Piricularia oryzae(rice blast). In addition to these properties they have a considerableeiiect against insects, for example soil insects or storage pests,against gastropodes, nematodes, particularly plant nematodes, such asPanagrellus redivivus, and can be used in certain concentrations againstundesirable plants. They also show an activity against human and animalpathogenic helmiths, for example trematodes ad cestodes, as well asagainst arachonoids (spiders, mites, ticks etc.).

The compounds of Formula I may be prepared by the methods known for thepreparation of carbamates by reacting araliphatic or heterocyclichydroxyl compounds or phenols of the formula HOR (a) withpara-chloro-meta-trifluoromethylphenyl iso cyanate in substance, inprotected form (as adduct with NaHSO or in situ,

(b) or with para-chloro-metal-trifluoromethylphenyl carbamic acid halideobtained by reacting parachlorometa-trifiuoroaniline and haloformic acidester.

The active substances of the present invention have antimicrobic,particularly antibacterial properties, for example against Gram-positiveorganisms, such as Staph. aureus as well as against acid-resistantbacteria, such as M. tuberculosis.

In aqueous dispersion they have an aflinity for keratin fibres andprotect the treated material from destruction by larvae of smallbutterflies (moths) and certain kinds of coleoptera (for example larvaeof Attagenus or Anthrenus). The carbamates of Formula I are suitable fordisinfection purposes and for the disinfecting cleaning of articles, forexample of cellulose-containing material. Such compounds can beprocessed to textile detergents and toilet soaps.

It is particularly advantageous that the compounds of Formula I do notshow any toxic side-effects towards warm-blooded animals in theconcentrations requiredfor disinfection. This makes it possbile to usethe new compounds for combating harmful organisms on a broad basis, forexample for the protection of timber, for preserving various industrialproducts, for protecting fibrous materials against harmfulmicroorganisms, for preserving agricultural products, as disinfectantsin veterinary medicine, in general hygiene and body care.

It is of particular importance that the compounds of the invention donot lose their bactericidal and fungicidal activity in the presence ofalbuminous substances and' soaps. The new compounds do not have anobjectionable odour of their own and are well tolerated, at least byhealthy skin.

Among the industrial products which may be preserved and/or disinfectedwith the help of the disinfectants according to the invention, thefollowing may be selected as examples: textile assistants or finishingagents, glues, binders, paints, thickeners, dyeing or printing pastesand similar preparations based on organic and inorganic dyestuffs orpigments, including those which contain casein or other organiccompounds as admixtures. Wall and ceiling paints, for example thosecontaining an albuminous colour binder, are also protected againstattack by pests by adding the new compounds.

Furthermore, the new compounds may be used for the protection of fibresand textiles by being absorbed on natural or synthetic fibres and theredeveloping a durable action against harmful organisms, for examplefungi, bac- 1 teria and insects. The compounds may be added before,simultaneously or after treatment of these textiles with othersubstances, for example dyeing or printing pastes, finishing agents andthe like. The compounds are in special measure able to protect woolfibres against moths and other ingestion pests. They show, for example,an excellent activity against moth larvae when applied to the fibre froman acetone solution or after absorption on the fibre from an aqueousbath in the presence of an emulsifier.

The compounds of Formula I may also be used as preservatives in thecellulose and paper industry, inter alia for preventing the known slimeformation caused by microorganisms in the apparatus used for theproduction of paper.

Depending on the nature of the additives with which the new activesubstances are combined in the agents according to the invention,preparations are obtained which are especially suitable for cleaning,disinfection or body care.

Thus, for example, detergents and cleansing agents having an excellentantibacterial or antimycotic effect are obtained by combining thecompounds according to the invention with detergents and/orsurface-active substances. The compounds of the Formula I may, forexample, be incorporated into soaps or be combined with soap-freedetergents and/ or surface-active substances, or they may be combinedwith mixtures of soaps and soapfree detergents.

The invention relates therefore also to the use of detergents andcleansing agents which contain as active component a compound of FormulaI, and also to making textile and non-textile materialsbacteria-resistant.

In most cases textile materials or synthetic or natural origin areprotected against infestation by bacteria by a content of 0.1 to 3% ofactive substance. The active substance may be used together with othertextile assistants, such as finishing agents, anti-creasing dressingsetc.

The preparations of the invention that contain the compounds of FormulaI may also be employed as cleansing agents in industry or in thehousehold, as well as in the food industry, e.g. dairies, breweries,abattoirs, in agriculture and in veterinary hygiene.

In general, the application forms correspond to the ordinaryformulations of pesticides; for example preparations that contain thecompounds of Formula I may also contain additives such as carriers,solvents, diluents, dispersants, wetting agents or adhesives as well asother pesticides.

The following examples illustrate the invention.

EXAMPLE 1 75 parts by weight of pentachlorphenol in 300 parts by volumeof acetonitrile and '67 parts by weight ofp-chloro-m-trifiuoromethylphenyl isocyanate in 100 parts by volume ofacetonitrile are mixed at 50 C. and 0.1 part of triethylenediamine isadded. The reaction mixture is allowed to stand for 3 hours at roomtemperature, then cooled and the product obtained is filtered off.

Compound No. 1 Cl 01 Melting point: 162-164 C. (from toluene).

In an analogous manner the following compounds of the type may beprepared:

Melting R1 point. C.

Compound number:

C1 Cl 162-164 C1 Cl Br Cl 4 OrN Cl 151-153 5 Br CH3 167-169 Br Br 7 BlBr 167-168 l BI CH3 -CHg-C H5 -91. 5

-CHr-Cl CH -NO:

12 CHz-(|]Hg 113-115 -CH;CH1 CH -OHr-Q TABLEContiuued Melting R1 point.C.

-CH J 17 Oil --C H-C H=CH l Decomposed.

EXAMPLE 2 In a greenhouse Cucurbita pepo L. plants were grown andsprayed once prophylactically with an aqueous broth of the test-productcontaining 0.1% of active substance of the Compound 3. Two days aftertreatment the plants were infected with spores of Erysiphecichoriacearum DC and after 12 to 14 days inspected as to infestationwith fungi. In comparison with the untreated control (0% effect) theeffect on the sprayed plants was 100% without phytotoxicity.

EXAMPLE 3 The new carbamates of the Formula I show a pronounced, strongeffect against Gram-positive bacteria, particularly againstStaphylococci and streptococci. They are also effective againstpathogenic fungi, for example Trihophyton interdigitale.

The antibacterial activity in the dilution test was determined asfollows:

Bacteriostasis and bacteriocidal activity 20 mg. of active substancewere dissolved in 10ml. of propylene-glycol; 0.25 ml. of this solutionwas added to 4.75 ml. of sterile glucose bouillon and then furtherdiluted in test-tubes in a ratio of 1:10. These solutions were theninoculated with Staphylococcus aureus and incubated for 48 hours at 37C. (Bacteriostasis). After 24 hours testtime 1 loop from these cultureswas spread on to glucose agar plates and incubated for 24 hours at 37 C.(Bacteriocidal activity). After the times mentioned the followinglimit-concentrations were determined in p.p.m. of the bateriostasis andbacteriocidal activity, respectively:

In order to test the antimycotic effect a solution of 1% strength of anactive compound in propylene-glycol was prepared and diluted with a 10%beer-wort solution in concentrations of 250, 100, 50, 30, 10, 3, 1 and0.5 p.p.m. The determination of the fungistatic limit concentration gavethe following values in p.p.m:

Aspergil lus Rttz'zppus maer mgrzcans Compound number:

6 EXAMPLE 5 In order to test the effect on gastropodes the followingaqueous dilution series of an active substance concentration wasprepared: 25, 12, 6, 4, 3, 2 and l p.p.m. Batches of 5 snails each(Australorbis glabratus) having a shell diameter of 15 mm. were put intoeach of these solutions for 24 hours at 20-22 C. They were then takenout and put for a further 48 hours in clear water with the addition offood. After this recuperation time the lethal rate was determined. ForCompound 1 the lethal rate was 100% in a concentration of 1.5 p.p.m.

EXAMPLE 6 In order to test the insecticidal effect young Phaseolusplants were dipped into aqueous active substance solutions containing0.2%, 0.1%, 0.08%, 0.04% and 0.02% of active substance, allowed to dryand infested with 5 larvae each of Orgyia gonostigma in the L-3 stage or5 larvae each of Epilachna varivestis in the L-4 stage; the whole ofeach of the plants then being covered with a plastic bag. The followingresults were obtained:

MORTALITIES WITH A CONCENTRATION OF 0.08% ACTIVE SUBSTANCE Compound No.16 is distinguished by its effect against Piricularia Oryzae B-ri. etCav., the causative agent of rice blast disease.

Rice plants were grown in a greenhouse and infected with an aqueousconidia suspension of the test fungus. The plants were incubated in ahumid chamber and on the day after infection sprayed with an aqueousbroth containing 0.1% of active substance.

After a week the treated plants showed an infestation of only 5% ascompared with a infestation of the control plants.

FORMULATION EXAMPLES Dusting preparations Equal parts of an activesubstance according to the invention and precipitated silicic acid arefinely ground. By mixing with kaolin or talcum, dusting preparations canbe prepared containing preferably l-6% of active substance.

Spraying powders For the preparation of a spraying powder the followingcomponents are, for example, mixed and finely ground:

50 parts of active substance according to the present invention 20 partsof Hisil (highly adsorbant silicic acid) 25 parts of bolus alba (kaolin)3.5 parts of the reaction product from para-tertiary octylphenol andethyleneoxide 1.5 parts of (sodium 1-benzyl-2-stearyl-benzimidazole-6,3'-disulphonate) 3,772,386 7 8 Emulsion concentrates wherein n is theinteger 0 or 1, and R represents phenyl optionally substituted withhalogen or nitro.

Readily soluble active substances may also be forrnu- 2. compoundsaccording to claim 1 in which n is 0- lated as emulsion concentratesaccording to the following prescriptions: 3. A compound according toclaim 1 of the formula 0 F 20 parts of active substance 5 3 70 parts ofxylene CH=CH 10 parts of a mixture from a reaction product of analkylphenol with ethyleneoxide and calcium dodecylbenzene ReferencesCited sulphonate 10 UNITED STATES PATENTS are mixed. On being dilutedwith water to the desired 3 609177 9/1971 Traber et a1 260 471 0concentration a sprayable emulsion is formed.

xvecclalmi d fth f 1 LORRAINE A. WEINBERGER, Primary Examiner g l S o eormu a 15 L. A. THAXTON, Assistant Examiner U.S. C1. X.R. C1-NH-CO-OCHz-(CH=CH)nR;

260-240 R, 295 CA, 347.4; 424263, 285, 300

